Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2688—Copolymers containing at least three different monomers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
  • C04B2111/00672—Pointing or jointing materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the present invention relates to cement-based dry mixes and their use.
• US-A-2003144386 describes the use of superabsorbents in cement-containing building material mixes for improving the strength development.
• the water uptake capacity or water retention capacity of the superabsorbents disclosed in this document is relatively low in calcium-containing systems, for example in cement-containing systems.
• U.S. Pat. No. 6,187,887 describes water-soluble or water-swellable copolymers containing sulpho groups which are used for increasing the water retention in building material systems. These copolymers differ from the essentially insoluble superabsorbents in that they are soluble in water and have very little if any water uptake capacity.
• the technologies disclosed in the abovementioned documents are in need of improvement in respect of their economics, in particular in respect of their yield.
• the desired economically advantageous, high-yield dry mixes should display good product properties both in the fresh state and in the cured state.
• a hydraulically setting dry mix preferably a tile adhesive in accordance with the standard EN 12004, characterized in that it comprises
• the polymer-modified dry mixes of the invention which contain a superabsorbent, pulverulent copolymer (superabsorbent) which is suitable for increasing the tolerance to high W/C values.
• the polymer chemistry of the superabsorbent has, according to the invention, been adapted so that a high water uptake capacity is ensured even in aqueous systems containing calcium ions, for example in the cement-containing, hydraulically setting systems according to the invention which additionally contain calcium ions from the calcium-containing accelerator salt.
• the use of increased amounts of the extremely cheap component water to increase the yield is possible for the first time by means of the dry mortars of the invention, as a result of which their economics are also significantly improved.
• dry mixes are frequently also referred to as dry mortars in the literature.
• the redispersible polymer powder c) is very particularly preferably present as vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl ester copolymer and/or vinyl acetate-vinyl ester-ethylene copolymer, with the vinyl ester monomers being selected in each case from the group consisting of vinyl laurate, vinyl pivalate and vinyl versatates, also as vinyl acetate-acrylic ester copolymer, vinyl acetate-acrylic ester-ethylene copolymer, styrene-butadiene copolymer and styrene-acrylic ester copolymer, with the acrylic esters in each case being esters of branched or unbranched alcohols having from 1 to 10 carbon atoms.
• the (co)polymers can additionally contain functional comonomer units in an amount of from 0.1 to 10% by weight, based on the total weight of the polymer.
• These functional comonomer units can be selected from the group consisting of monocarboxylic or dicarboxylic acids, for example (meth)acrylic acid and/or maleic acid; the group consisting of ethylenically unsaturated carboxamides such as (meth)acrylamide; from the group consisting of ethylenically unsaturated sulphonic acids and salts thereof, preferably vinylsulphonic acid and/or styrene-sulphonic acid; from the group consisting of multiply ethylenically unsaturated comonomers, for example divinyl adipate, triallyl isocyanurate, diallyl maleate and/or allyl methacrylate.
• the proportion of structural units containing a (meth)-acrylamido group in the redispersible polymer powders of the general formula II is preferably less than 25 mol %.
• the (co)polymerization is carried out by processes well known in the industry, e.g. the emulsion polymerization process.
• the dispersions obtained can be stabilized either by means of an emulsifier or by means of a protective colloid such as polyvinyl alcohol.
• drying is carried out, usually by conventional processes such as spray drying, freeze drying, coagulation of the dispersion and subsequent fluidized-bed drying.
• the preferred process is spray drying.
• the redispersible polymer powders are present in the hydraulically setting dry mix in an amount of from 0.5 to 10% by weight, preferably from 0.8 to 7% by weight, particularly preferably from 1.0 to 4% by weight.
• the superabsorbent copolymers hold water or salt solutions containing calcium ions as are present in the building material mixes as hydrogel in microregions.
• the amount of (make-up) water and thus also the volume of the ready-to-use building material mix can be increased significantly.
• the dry mixes containing superabsorbent copolymers according to the invention or the building material mixes formed by addition of water therefore have the advantage that they have a particularly high yield and are particularly economically advantageous.
• Further customary additives such as air pore formers, antifoams, polyacrylamides, acrylate-based thickeners, functional sheet silicates, plasticizers customary for cement-containing systems, for example polycarboxylate ethers (PCE), melamine-formal dehydesulphonates (MFS), ⁇ -naphthalene-formaldehydesulphonates (BNS) and fibres such as cellulose fibres or synthetic fibres (e.g. aramid fibres) can also be present in the dry mixes of the invention.
• PCE polycarboxylate ethers
• MFS melamine-formal dehydesulphonates
• BNS ⁇ -naphthalene-formaldehydesulphonates
• fibres such as cellulose fibres or synthetic fibres (e
• the dry mixes comprise
• the water-soluble copolymers containing sulpho groups g) will be described in more detail below.
• the copolymers g) represent further water retention agents and differ from the above-described polysaccharide-based water retention agents and the preferably water-insoluble anionic, superabsorbent copolymers f a ) which have likewise been described above.
• the water-soluble copolymers containing sulpho groups are preferably used in powder form in the dry mix. They contain structural units of the general formulae I and II, with at least one further structural unit selected from among the structural units IV and V being present.
• the copolymers may comprise structural units of the general formulae I, II, IV or structural units of the general formulae I, II, V or structural units of the general formulae I, II, IV, V.
• the proportion of structural units of the general formulae I and II in the water-soluble copolymer containing sulpho groups is in each case in the range from 3 to 96 molpercent, that of the structural units of the general formula IV is in the range from 0.001 to 10 molpercent and that of the structural units of the general formula V is in the range from 0.1 to 30 molpercent.
• Preferred copolymers contain from 30 to 80 molpercent of structural units of the general formula I and from 5 to 50 molpercent of structural units of the general formula II, also from 0.1 to 5 molpercent of structural units of the general formula IV or from 0.2 to 15 molpercent of structural units of the general formula V, or else both structural units IV and V in the corresponding, abovementioned amounts.
• the structural unit of the general formula I is preferably derived from monomers such as 2-acrylamido-2-methylpropanesulphonic acid, 2-methacrylamido-2-methylpropane-sulphonic acid.
• Particular preference is given to 2-acrylamido-2-methylpropanesulphonic acid and its salt compounds.
• the structural unit of the general formula II is preferably derived from monomers such as acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylol-acrylamide, N-tert-butylacrylamide.
• the structural unit of the general formula IV is preferably derived from monomers such as tristyrylphenolpolyethylene glycol 1100 methacrylate, behenylpolyethylene glycol 1100 methacrylate, stearylpolyethylene glycol 1100 methacrylate, tristyrylphenol-polyethylene glycol 1100 acrylate, tristyrylphenolpolyethene glycol 1100 monovinyl ether, behenylpolyethene glycol 1100 monovinyl ether, stearylpolyethene glycol 1100 monovinyl ether, tristyrylphenolpolyethylene glycol 1100 vinyloxybutyl ether, behenylpolyethylene glycol 1100 vinyloxybutyl ether, tristyrylphenolpolyethylene glycol-block-propylene glycol allyl ether, behenylpolyethylene glycol-block-propylene glycol allyl ether, behenylpolyethylene glycol-block-propylene
• the structural unit of the general formula V is preferably derived from monomers such as allylpolyethylene glycol (350 to 2000), methylpolyethylene glycol (350 to 2000) monovinyl ether, polyethylene glycol (500 to 5000) vinyloxybutyl ether, polyethylene glycol-block-propylene glycol (500 to 5000) vinyloxybutyl ether and methyl-polyethylene glycol-block-propylene glycol allyl ether.
• monomers such as allylpolyethylene glycol (350 to 2000), methylpolyethylene glycol (350 to 2000) monovinyl ether, polyethylene glycol (500 to 5000) vinyloxybutyl ether, polyethylene glycol-block-propylene glycol (500 to 5000) vinyloxybutyl ether and methyl-polyethylene glycol-block-propylene glycol allyl ether.
• copolymers used according to the invention are prepared in a manner known per se by linking of the monomers derived from the corresponding structural units I, II, IV and V by means of free-radical, bulk, solution, gel, emulsion, dispersion or suspension polymerization. It has been found to be advantageous to set the number of structural units so that the water-soluble copolymers containing sulpho groups g) have a number average molecular weight of from 50 000 to 20 000 000.
• the water-soluble copolymers containing sulpho groups g) are preferably present in the dry mix in an amount of from 0.1 to 1.5% by weight, particularly preferably from 0.3 to 1.2% by weight and very particularly preferably from 0.5 to 1.0% by weight.
• the dry mixes of the invention comprise
• the cationic copolymers h will be described in more detail below.
• the water-soluble cationic copolymers h) represent further water retention agents and differ from the above-described polysaccharide-based water retention agents and the preferably water-insoluble cationic, superabsorbent copolymers f b ) which have likewise been described above.
• the water-soluble cationic copolymers are preferably used in powder form in the dry mix. These water-soluble cationic copolymers enable considerable improvements in the water retention to be achieved in aqueous building material systems based on hydraulic binders such as cement even in the case of high salt contents.
• the rheological modification, the water retention capacity, the stickiness and the processing properties can be optimally set for the respective application via the composition of the copolymers.
• the good solubility in water which is necessary for use of the copolymers in aqueous building material applications is ensured, in particular, by the cationic structural unit of the general formula VI.
• the uncharged structural unit of the general formulae VIIa and/or VIIb is required mainly for construction of the main chain and achievement of suitable chain lengths, while the hydrophobic structural units of the general formula VIII make associative thickening, which is advantageous for the desired product properties, possible.
• the structural unit of the general formula VI preferably results from polymerization of one or more monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium salts, [2-(methacryloyloxy)-ethyl]trimethylammonium salts, [3-(acryloylamino)propyl]trimethylammonium salts.
• [3-(methacryloylamino)propyl]trimethylammonium salts N-(3-sulphopropyl)-N-methyl-acryloxyethyl-N,N-dimethylammonium betaine, N-(3-sulphopropyl)-N-methyacryl-amidopropyl-N,N-dimethylammonium betaine and/or 1-(3-sulphopropyl)-2-vinyl-pyridinium betaine.
• the salts mentioned are preferably present as halides or methosulphates.
• the structural unit of the general formula VIIa preferably results from polymerization of one or more of the monomer species acrylamide, methacrylamide, N-methyl-acrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-tert-butyl acrylamide, etc.
• monomers as basis of the structure VIIb are N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam and/or N-vinylpyrrolidone-5-carboxylic acid.
• the structural unit of the general formula VIII preferably results from polymerization of one or more of the monomer species tristyrylphenolpolyethylene glycol 1100 methacrylate, tristyrylphenolpolyethylene glycol 1100 acrylate, tristyrylphenolpolyethene glycol 1100 monovinyl ether, tristyrylphenolpolyethylene glycol 1100 vinyloxybutyl ether and/or tristyrylphenolpolyethylene glycol-block-propylene glycol allyl ether.
• the structural units of the general formula VI are present in the copolymer in a proportion of from 15 to 50 molpercent, those of the general formula VIIIa and/or VIIb are present in a proportion of from 30 to 75 molpercent and those of the general formula VIII are present in a proportion of from 0.03 to 1 molpercent.
• the copolymers h) according to the invention are preferably prepared in a manner known per se by linking of the monomers forming the structural units of the general formulae VI, VIIa and/or VIIb and VIII and if appropriate further monomers by means of free-radical polymerization. Since the products used according to the invention are water-soluble copolymers, polymerization in the aqueous phase, polymerization in an inverted emulsion or polymerization in inverse suspension is preferred. The copolymers are advantageously prepared by gel polymerization in the aqueous phase.
• the water-soluble cationic copolymers h) are preferably present in the dry mix in an amount of from 0.1 to 1.5% by weight, particularly preferably from 0.3 to 1.2% by weight and very particularly preferably from 0.5 to 1.0% by weight.
• the building material mix of the invention is preferably used as tile adhesive in accordance with DIN EN 12004, as sealing slurry, joint filler in accordance with EN 13888, repair mortar in accordance with EN 1504, knifing filler, parquet adhesive, screed, plaster or render in accordance with EN 998-1 and as adhesive mortar or reinforcing mortar for composite thermal insulation systems (CTIS) in accordance with EN 13499 and EN 13500.
• repair mortars are, for example, mortars for the repair or replacement of damaged concrete.
• Knifing fillers serve, for example, for final working of a substrate to obtain flat surfaces (walls or ceilings).
• Composite thermal insulation systems are insulation systems which are usually employed on the building site using factory-made thermal insulation materials. They are fixed in place by means of adhesive mortar; if mechanical fastening (reinforcement) is to be applied, the system is referred to as reinforcing mortar.
• the determination of the uptake capacity of the superabsorbents according to the invention is carried out in accordance with the standard edana 440.2-02 developed for the hygiene industry with modification of the method, i.e. replacement of the 0.9 percent strength sodium chloride solution specified there as test liquid by a one percent strength calcium formate solution.
• This method also referred to as “tea bag test”, is carried out by welding a defined amount (about 200 mg) of superabsorbent polymer into a tea bag and dipping it into a one percent strength calcium formate solution for 30 minutes. The tea bag is subsequently allowed to drip for five minutes and is weighed. A tea bag without superabsorbent polymer is concomitantly tested as blank.
• Uptake capacity (final weight ⁇ blank ⁇ initial weight)/initial weight(g/g) Determination of the Proportion of Extractable Material in the Superabsorbent Copolymers
• the proportion of extractable material is determined by extraction of the superabsorbent copolymer in 0.9 percent strength sodium chloride solution with subsequent determination of total organic carbon (TOC determination). For this purpose, 1.0 g of the superabsorbent polymer is left to stand for sixteen hours in one litre of 0.9 percent strength by weight sodium chloride solution and subsequently filtered off. After determination of the TOC content of the filtrate, the proportion of extractable material is calculated via the known carbon content of the superabsorbent polymer.
• Copolymer 1 (Anionic Superabsorbent Copolymer)
• the solution was transferred to a plastic container having dimensions (w ⁇ d ⁇ h) of 15 cm ⁇ 10 cm ⁇ 20 cm and 16 g of one percent strength 2,2′-azobis(2-amidinopropane) dihydrochloride solution, 20 g of one percent strength sodium peroxodisulphate solution, 0.7 g of one percent strength Rongalit C solution, 16.2 g of 0.1 percent strength tert-butyl hydroperoxide solution and 2.5 g of 0.1 percent strength Fe(II) sulphate heptahydrate solution were subsequently added in succession.
• the copolymerization was initiated by radiation with UV light (two Philips tubes; Cleo Performance 40 W).
• the now hard gel is taken from the plastic container and cut into cubes having an edge length of about 5 cm by means of scissors.
• the release agent Sitren 595 polydimethylsiloxane emulsion; from Goldschmidt.
• the release agent was a polydimethylsiloxane emulsion which was diluted with water in a ratio of one to twenty.
• the resulting gel granules of copolymer 1 were uniformly distributed over a drying mesh and dried to constant weight at about 120-140° C. in a convection drying oven. This gave about 375 g of white, hard granules which were converted into a pulverulent state by means of a centrifugal mill.
• the average particle diameter of the polymer powder was from 30 to 50 ⁇ m and the proportion of particles which did not pass a sieve having a mesh size of 63 ⁇ m was less than 2% by weight.
• the uptake capacity of the copolymer 1 in a one percent strength calcium formate solution is 32 g/g and the proportion of extractable material is 7.0 percent.
• the product has been found to be shear stable and, in particular, displays no after-thickening, e.g. in the tile adhesive.
• the copolymer 1 reaches its maximum water uptake capacity within four minutes, which corresponds approximately to the customary times over which cement-containing building material mixes are mixed with water.
• Copolymer 2 (Cationic Superabsorbent Copolymer)
• the solution was transferred to a plastic container having dimensions (w ⁇ d ⁇ h) of 15 cm ⁇ 10 cm ⁇ 20 cm and 16 g of one percent strength 2,2′-azobis(2-amidinopropane) dihydrochloride solution, 20 g of one percent strength sodium peroxodisulphate solution, 0.7 g of one percent strength Rongalit C solution, 16.2 g of 0.1 percent strength tert-butyl hydroperoxide solution and 2.5 g of 0.1 percent strength Fe(II) sulphate heptahydrate solution were subsequently added in succession.
• the polymerization was initiated by radiation with UV light (two Philips tubes; Cleo Performance 40 W).
• the hard gel was taken from the plastic container and processed further in the same way as described above for copolymer 1. This gave about 375 g of white, hard granules which were converted into a pulverulent state by means of a centrifugal mill.
• the average particle diameter of the polymer powder was from 30 to 50 ⁇ m and the proportion of particles which did not pass a sieve having a mesh size of 63 ⁇ m was less than 2% by weight.
• the uptake capacity of the copolymer 2 in a one percent strength calcium formate solution is 29 g/g and the proportion of extractable material is 9.0 percent.
• the comparative polymer 1 viz. Luquasorb® 3746 SX from BASF AG, is a crosslinked partially neutralized sodium polyacrylate. In a one percent strength calcium formate solution, the gel collapses, i.e. virtually complete loss of the absorption capacity occurs.
• the comparative polymer 2 viz. Luquasorb® AF 2 from BASF AG, is a crosslinked copolymer of acrylamide and acrylic acid, with the acrylic acid having been neutralized by means of sodium hydroxide.
• the commercial product Luquasorb® AF 2 1000-3000 ⁇ m was milled by means of a centrifugal mill so that the proportion of particles which do not pass a sieve having a mesh size of 63 ⁇ m was less than 2% by weight.
• the product was prepared by the gel polymerization process.
• the uptake capacity is 10 g/g.
• Comparative Examples 1 and 2, 3 In contrast to Comparative Examples 1 (without superabsorbent) and 2, 3 (with comparative superabsorbents respectively), the maximum amount of water which can be used in the case of the superabsorbent according to the invention copolymer 1 of Example 1 while still fulfilling the standard 1308 (slippage resistance of tile adhesive mortars) is significantly higher. The yield is accordingly significantly higher.
• the water requirement in Comparative Examples 2 and 3 is close to that of Comparative Example 1 (without superabsorbent), i.e. the superabsorbents which are not according to the invention of Comparative Examples 2 and 3 have only a very small water uptake capacity.
• the correctability of a stoneware tile is a test which indicates the ease or difficulty with which the position of a strongly water-absorbing tile can be corrected after a particular time interval (usually 5, 10 or 15 minutes) after being placed on the adhesive bed.
• the correctability after 10 minutes is improved at least over Comparative Example 1.
• the skin formation time is likewise improved over Comparative Example 1 and, despite the greater amount of make-up water in Example 1, a skin formation time similar to Comparative Example 2 was found.
• the skin formation time is defined as the time after making-up of the tile adhesive mortar after which a skin is formed on the bed of adhesive. It is determined visually.
• the air pore content of the tile adhesives in Table 1 ranged from 21 to 24 percent.
• the comparative polymer 1 (Comparative Example 5) thus does not have an effect as produced according to the invention.
• Comparative Example 3 shows that good adhesive pull strengths which are similar to those in the examples according to the invention can be achieved only by the use of higher and therefore economically unfavourable amounts of redispersible polymer powder.
• the amounts of cellulose ether used could be reduced somewhat in the examples according to the invention.
• the results for the adhesive open time (Examples 2 to 5) are somewhat better than in Comparative Example 3 in which a large amount of redispersible polymer powder is used; compared to Comparative Examples 4 and 5, they are improved significantly.
• the use of the anionic copolymer 1 according to the invention (Examples 6 and 7) or of the cationic polymer 2 according to the invention (Examples 8 and 9) and halving of the amount of redispersible polymer powder (compared to Comparative Example 6) does not have any adverse effects on the adhesive pull strengths.
• the adhesive pull strengths do not deteriorate during dry storage and during hot storage, in contrast to Comparative Example 7.
• Comparative Example 6 is less economically favourable because of the relatively large amounts of redispersible dispersion powder.
• the adhesive open time and the adhesive pull strengths after 20 minutes are significantly improved in Examples 6 to 9 according to the invention compared to Comparative Example 7.

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